Process for forming a phosphate conversion coating on metal

ABSTRACT

A metal surface on which a phosphate conversion coating is to be formed and which has been surface conditioned by contact with a liquid surface conditioner composition that contains dispersed fine particles of solid phosphate of at least one divalent or trivalent cations type and an adhesion promoting agent. After such conditioning, a very high quality conversion coating can be formed on the surface by contact with a nickel-free liquid phosphating composition that contains at least acid, zinc cations, and phosphate anions and optionally and preferably also contains other materials.

This application claims priority from International Application No.PCT/US00/22335, filed Aug. 16, 2000 and published in English, andJapanese Application No. H11-230060, filed Aug. 16, 1999.

FIELD AND BACKGROUND OF THE INVENTION

This invention relates to processes for the phosphate conversiontreatment of metals wherein said processes employ a nickel ion-freephosphate conversion treatment bath and produce a uniform, stronglypaint-adherent, and highly post-painting corrosion-resistant coating onsuch metals as steel sheet, zinc-plated steel sheet, aluminum alloys,and magnesium alloys.

Phosphate conversion treatments are currently executed as a pre-painttreatment on automotive body components in order to enhance corrosionresistance and improve the steel sheet-to-paint adherence. In thesephosphate conversion treatments, the metal is first brought into contactwith a colloidal titanium surface conditioning bath and is then broughtinto contact with an acidic solution containing phosphate ions, zincions, nickel ions, and manganese ions in order to precipitate aphosphate coating on the metal.

However, in association with today's heightened concern withenvironmental protection, the regulatory situation with regard to nickelin wastewater has become increasingly stringent, particularly in Europe.It is certainly prudent to anticipate that regulations on nickel inwastewater might also become much more demanding in other countries inthe future. These considerations make it desirable to eliminate thenickel from the conversion treatment baths used in zinc phosphatetreatments.

Unfortunately, a number of negative effects are caused by removal of thenickel from many phosphate treatment baths used in the aforementionedphosphate treatment processes: The crystals in the phosphate coatingundergo coarsening: the phosphate coating suffers from a loss ofuniformity, the post-painting corrosion resistance declines, and thesecondary (water-resistant) adherence of paint to zinc-plated materialalso declines,

Japanese Laid Open Patent Application (PCT) Number Hei 7-505445(505,445/1995) teaches a nickel-free phosphate treatment process inorder to solve the problems referenced above. This treatment processinvolves formation of a nickel-free phosphate coating by treatment witha phosphate conversion bath containing 0.2 to 2 grams of zinc ions perliter of bath (this unit of concentration being freely used hereinafterfor any constituent of any liquid and being usually abbreviated as“g/l”), 0.5 to 25 milligrams of copper ions per liter, and 5 to 30 g/lphosphate ions. This process uses copper as a substitute metal fornickel, but still suffers from several problems. Since the allowablecopper level in this conversion treatment bath is so very low,management of the copper concentration in real-world lines isexceedingly difficult. Another concern is with electrolytic corrosion ofthe equipment accompanied by displacement copper plating on parts of theequipment.

Given this background, there is a desire for development of a phosphateconversion treatment process that does not use nickel but neverthelessaffords a post-painting adherence and post-painting corrosion resistancethat are the equal of those afforded by existing phosphate conversiontreatments that use nickel. One major object of this invention is toprovide a phosphate conversion treatment process that treats metalsurfaces with a nickel-free conversion treatment bath and produces aphosphate conversion coating that evidences an excellent post-paintingcorrosion resistance and excellent paint adherence.

BRIEF SUMMARY OF THE INVENTION

It has been found that most or all of the problems caused by the removalof nickel from previous phosphating treatments can be eliminated byusing a surface conditioning composition that contains very fine,dispersed solid phosphate particles.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

More specifically, a process according to the invention for forming aphosphate conversion on a metal substrate surface comprises, preferablyconsists essentially of, or more preferably consists of the followingoperations:

(I) contacting the metal substrate surface with an aqueous liquidsurface conditioning composition (hereinafter for brevity often called a“bath” without intending any implication that it must be contacted withthe metal substrate by immersion of the metal substrate in a volume ofthe aqueous liquid surface conditioning composition) that comprises,preferably consists essentially of, or more preferably consists of,water and the following components:

(I.A) dispersed solid phosphate particles that:

(i) have a diameter no greater than 5 micrometres, this unit of lengthbeing hereinafter usually abbreviated as “μm”; and

(ii) comprise, preferably consist essentially of, or more preferablyconsist of, at least one substance selected from the group consisting ofphosphates that contain at least one divalent or trivalent metal cation;and

(I.B) as adhesion-promoting component, at least one selection from thegroup consisting of the following subgroups:

(1) monosaccharides, polysaccharides, and derivatives thereof;

(2) phosphorus containing solutes selected from the group consisting oforthophosphoric acid, condensed phosphoric acids, and organophosphonicacid compounds;

(3) water-soluble polymers that are homopolymers or copolymers of vinylacetate and derivatives of these homopolymers and copolymers; and

(4) copolymers and polymers as afforded by the polymerization of:

(a) at least one selection from:

monomers, exclusive of vinyl acetate, that conform to general chemicalformula (I):

 where R¹=H or CH₃ and R²=H, C₁ to C₅ alkyl or C₁ to C₅ hydroxyalkyl;and

other α,β-unsaturated carboxylic acid monomers; and, optionally,

(b) not more than 50 % by weight of monomers that are not vinyl acetateand are not within the description of part (a) immediately above but arecopolymerizable with said monomers that are within the description ofsaid part (a); and

(II) contacting the metal substrate surface as conditioned in operation(I) as described above with a nickel-free phosphate conversion treatmentbath that comprises, preferably consists essentially of, or morepreferably consists of water and the following amounts of the followingcomponents:

(II.A) from 0.5 to 5 g/l of zinc cations;

(II.B) from 5 to 30 g/l of phosphate ions; and

(II.C) a component of conversion accelerator.

In a preferred embodiment, the above-specified conversion treatmentbaths also contain from 0.1 to 3.0 g/l of at least one type of metalcontaining ions selected from the group consisting of magnesium ions,cobalt ions, manganese ions, calcium ions, tungstate ions, and strontiumions.

The features of this invention are explained in greater detailhereinbelow. Whenever a group of materials from which a constituent canbe selected is specified, whether by a specific list, use of genericchemical terms, and/or conformance to a general chemical formula, anytwo or more of the group may be selected instead of a single member withequal preference unless explicitly stated otherwise.

While no particular limitations apply to the metal on which theinventive phosphate-treatment process may be executed, this metal ispreferably steel sheet, zinc-plated steel sheet, zinc alloy-plated steelsheet, magnesium alloy, or aluminum alloy.

It is preferred in the practice of the invention that the metalsubstrate surface be clean prior to the phosphate conversion treatment.Metal whose surface is already clean can be brought without furthertreatment into contact with the surface conditioning bath. However, inthe case of treatment of metal whose surface is contaminated withadherent materials such as iron particles, dust, and oil, thecontaminants adhering on the surface should be removed by cleaning, forexample, by cleaning with a water-based alkaline degreaser or anemulsion degreaser or by solvent degreasing. When a water-based cleaneris used, the cleaning bath remaining on the metal surface is preferablyremoved by the provision of, for example, a water rinse step after thecleaning step.

At least some of the particles of divalent and/or trivalent metalphosphate present in a surface conditioning bath in a process accordingto the invention must have a particle size or diameter no greater than 5μm. (Insolubles of larger size are undesirable because—depending on theparticular circumstances—they often cannot be stably maintained in theaqueous bath.) These phosphate particles are believed to function asnuclei during phosphate crystal deposition and also to promote thedeposition reaction itself, by undergoing partial dissolution in thephosphate conversion treatment bath and inducing a substantialacceleration of the initial phosphate crystal deposition reactions bysupplying one or more main components of the phosphate crystals to theregion immediately adjacent to the metal surface.

The divalent and trivalent metals used here are not critical, butpreferably comprise at least one selection from Zn, Fe, Mn, Co, Ca, Mg,and Al. The divalent and/or trivalent metal phosphate particles arepreferably present at a concentration from 0.001 to 30 g/l. Accelerationof the initial phosphate crystal deposition reactions does not normallyoccur at a divalent and/or trivalent metal phosphate particleconcentration below 0.001 g/l due to the small amount of divalent and/ortrivalent metal phosphate particles that become adsorbed on the metalsurface at such low concentrations. Concentrations below 0.001 g/l alsoprevent acceleration of the crystal deposition reactions due to thesmall number of divalent and/or trivalent metal phosphate particlesavailable to act as crystal nuclei. Divalent and/or trivalent metalphosphate particle concentrations in excess of 30 g/l cannot be expectedto provide additional promotion of the phosphate conversion reactionsand hence will be uneconomical.

The adhesion-promoting component that must be present in the inventivesurface conditioning bath functions to improve the dispersion stabilityof the divalent and/or trivalent metal phosphate particles and toaccelerate adsorption of the divalent and/or trivalent metal phosphateparticles onto the metal surface. More specifically, the adhesionpromoting component is believed to adsorb on the surface of the divalentand/or trivalent metal phosphate particles and, through a sterichindrance activity and repulsive forces arising from its electricalcharge, to prevent collisions among the divalent and/or trivalent metalphosphate particles in the surface conditioning bath and thereby inhibittheir aggregation and sedirmentation. In addition, due to its structure,the adhesion-promotng component itself is believed to have an ability toadsorb to metal surfaces and thereby to accelerate adsorption to metalsurfaces by the divalent and/or trivalent metal phosphate particles, sothat the surface conditioning activity. manifests upon contact betweenthe metal workpiece and surface conditioning bath.

The adhesion-promoting component concentration is preferably from 1 to2,000 parts by weight of the adhesion promoting component per 1000 partsby weight of the total conditioning composition, this unit ofconcentration being hereinafter usually abbreviated as “ppm”. Atconcentrations below 1 ppm a surface conditioning activity can notusually be produced just by contact between the metal workpiece and thesurface conditioning bath. Not only can no additional benefit beexpected at concentrations in excess of 2,000 ppm, but suchconcentrations can impair the phosphate conversion coating formed,perhaps as a result of excessive adsorption of the adhesion promotingcomponent on the metal substrate surface.

A saccharide type of adhesion-promoting component for the surfaceconditioning operation in a process according to the invention may beexemplified by fructose, tagatose, psicose, sorbose, erythrose, threose,ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose,gulose, idose, galactose, talose, and the sodium and ammonium salts ofall of these saccharides.

A phosphorus containing acid type of adhesion-promoting component in thesurface conditioning process is exemplified by orthophosphoric acid,polyphosphoric acids, and organophosphonic acid compounds, or moreindividually by pyrophosphoric acid, triphosphoric acid,trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoricacid, aminotrimethylenephosphonic acid,1-hydrbxyethylidene-1,1-diphosphonic acid,ethylenediaminetetramethylenephosphonic acid,diethylenetriaminepentamethylenephosphonic acid, and the sodium andammonium salts of all of the preceding acids. Sodium salts are preferredfor the organophosphonic acids if they are to be used in salt form.

Polymeric adhesion promoting components derived from polyvinylacetate ina surface conditioning operation in a process according to the inventionare exemplified by polyvinyl alcohols afforded by the hydrolysis ofvinyl acetate polymers, cyanoethylated polyvinyl alcohols afforded bythe cyanoethylation of polyvinyl alcohol with acrylonitrile, formalatedpolyvinyl alcohols afforded by the acetalation of polyvinyl alcohol withformaldehyde, urethanized polyvinyl alcohols afforded by theurethanation of polyvinyl alcohol with urea, and water-soluble polymersafforded by the introduction of carboxyl moieties, sulfonic moieties, oramide moieties into polyvinyl alcohol. Suitable vinylacetate-copolymerizable monomers are exemplified by acrylic acid,crotonic acid, and maleic anhydride. The effects associated with thepresent invention will be fully manifested as long as the vinyl acetatepolymer or derivative thereof or the copolymer of vinyl acetate andvinyl acetate-copolymerizable monomer is soluble in water. Within thislimitation, these effects are independent of the degree ofpolymerization and the degree of functional group introduction of thesubject polymers.

Suitable monomers for other polymeric adhesion promoting components forthe surface conditioning operation are exemplifed by: methyl acrylate,ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate,hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate,hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxymethylmethacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate,hydroxybutyl methacrylate, and hydroxypentyl methacrylate as examples ofpolymers according to formula (I); acrylic acid, methacrylic acid, andmaleic acid as unsaturated adds; and styrene, vinyl chloride, andvinylsulfonic acid as optional comonomers.

A surface conditioning bath used by the inventive phosphate treatmentprocesses can also optionally contain an alkali metal salt or ammoniumsalt or a mixture thereof, selected from the group consisting oforthophosphate salts, metaphosphate salts, orthosilicate salts,metasilicate salts, carbonate salts, bicarbonate salts, nitrate salts,nitrite salts, sulfate salts, borate salts, organic acid salts, andcombinations of two or more selections from the aforesaid alkali metaland ammonium salts. The concentration of this component is not critical,but when used is preferably from 0.5 to 20 g/l. The surface conditioningbath may also contain a surfactant to promote uniform wetting of thesurface being treated.

The phosphate conversion treatment process of this invention will now beconsidered in greater detail. A zinc ions concentration below 0.5 g/l,because it can prevent the formation of a coating of acceptable weightand can result in a diminished coverage ratio by the deposited phosphatecrystals, can produce an inadequate post-painting corrosion resistance.A zinc ions concentration in excess of 5.0 g/l can cause a coarsening ofthe coating crystals, resulting in particular in a decline in thepost-painting adherence. The use of a phosphate ions concentration below5.0 g/l strongly impairs the production of a normal conversion coating.Concentrations in excess of 30.0 g/l are uneconomical since they provideno additional effect. Phosphate ions can be supplied by the addition ofphosphoric acid or its aqueous solution to the phosphate conversiontreatment bath or by the dissolution of, for example, sodium, magnesium,or zinc phosphate in the phosphate conversion treatment bath.

The conversion treatment bath also contains a component known as a“conversion accelerator” or simply “accelerator”. The accelerator actsto restrain gaseous hydrogen production during etching, an actionsometimes called “depolarizing” the metal substrate surface. Otherwise,however, no particular limitations apply to the accelerator; and anymaterial or combination of materials recognized as a conversionaccelerator in prior art may be used.

The phosphate conversion treatment bath of this invention can alsocontain from 0.1 to 3.0 g/l of at least one type of metal containingions selected from the group consisting of magnesium cations, cobaltcations, manganese cations, calcium cations, tungstate anions, andstrontium cations. The presence of this component in the phosphateconversion treatment bath, through its incorporation into the phosphatecoating and through its precipitation in a form separate from thephosphate, provides additional performance enhancements in thepost-painting corrosion resistance and post-painting adherence,respectively. The use of a concentration below 0.1 g/l usually does noteffect any improvement in painting performance. A concentration above3.0 g/l is economically wasteful, since no additional improvements inpainting performance usually results; a high concentration can actuallyhinder deposition of the zinc phosphate that is the main component of aneffectively protective conversion coating produced according to thisinvention. The source of one of the types of metal cations can be, forexample, an oxide, hydroxide, carbonate, sulfate, nitrate, or phosphateof the particular metal. The source of tungstate can be, for example,the sodium or potassium salt.

An etchant may be added to the phosphate conversion treatment bath inorder to induce a uniform etch of the surface of the metal workpiece.Usable as this etchant are, for example, fluoride ions and complexfluoride ions such as fluorosilicate ions. The fluorine compound usedhere can be, for example, hydrofluoric acid, fluorosilicic acid, or awater soluble metal saft (e.g., sodium salt, potassium salt) of thepreceding.

The phosphate conversion treatment can be carried out by immersion orspraying or some combination thereof. Treatment for about 1 to 5 minutescan form a conversion coating satisfactorily robust for practicalapplications. The temperature of the phosphate conversion treatment bathis preferably from 30 to 60° C.

The phosphate conversion treatment is preferably followed by at leastone water rinse, and deionized water is preferably used in the finalwater rinse.

Working and comparative examples of actual treatments are provided belowin order to demonstrate the advantageous effects of this invention inspecific terms. The working examples that follow are simply examples ofthe application of the invention, and in no way limit the applicationsof the invention or materials usable in the application of theinvention.

Materials Tested

The following metal substrates were treated in the working andcomparative examples: electrogalvanized steel sheet (“EG”), sheetthickness=0.8 millimeters (hereinafter usually abbreviated as “mm”),plating add-on=20 grams of plated zinc per square meter of sheetsurface, this unit of coating weight being hereinafter freely used forany coating on any surface and being hereinafter usually abbreviated as“g/m²; galvannealed hot-dip galvanized steel sheet (“GA”), sheetthickness=0.8 mm, coating add-on=45 g/m²; and cold-rolled steel sheet(“CRS”), sheet thickness=0.8 mm, type SPCC-SD.

Treatment operations sequence (common to the working and comparativeexamples; as noted in the description of the testing below, not all ofthe specimens tested were subjected to the operations numbered 8 orhigher)

(1) Degreasing with diluted FINECLEANER® L4460 alkaline degreaserconcentrate, a product of Nihon Parkerizing Co., Ltd., the workingdegreaser containing 20 g/l of agent A and 12 g/l of agent B, 43° C.,120 seconds, dipping.

(2) Water rinse with tapwater ambient temperature, 30 seconds, spray.

(3) Surface conditioning

The conditions are described below in the tables for the working andcomparative examples. The colloidal titanium surface conditioningtreatments were run using PREPALENE® ZN, a product of Nihon ParkerizingCo., Ltd.

(4) Phosphate conversion treatment

The conditions are described below in the tables for the working andcomparative examples. The treatment time was 120 seconds in all cases.

(5) Water rinse (tapwater): ambient temperature, 30 seconds, spray

(6) Deionized water rinse (deionized water with an electricalconductivity ≦0.2 microSiemens per centimeter): ambient temperature, 20seconds, spray

(7) Drain/dry: 120 seconds, forced hot air at 90° C.

(8) Cationic electrocoating to a film thickness of about 20 μm, thenbake for 20 minutes at 180° C.

(9) Surface coating with a film thickness of about 40 μm baked for 20minutes at 140 ° C.

(10 ) Top coating with a film thickness of about 40 μm baked for 20minutes at 140° C.

Test and Other Evaluation Methods

The coating appearance was evaluated on the following two-level scale(after operation (7) as described above:

+: the coating was uniform;

x: the coating exhibited a significant lack of uniformity with visiblevoids.

The test conditions and evaluation scale for the secondary(water-resistant) adherence were as follows: The sheet after operation(10) as described above was immersed for 240 hours in a hot water bath(maintained at 40° C.) that was being bubbled with air. The sheet wasallowed to stand for 2 hours after removal from the hot water bath,after which time the peeling behavior was evaluated by cutting a grid (2mm on each edge) in the sheet and subjecting this to tape peeling. Thepeeling behavior was evaluated using the following three-level scale:

++: complete absence of peeling;

+: some peeling observed at the edges of the grid cut;

x: substantial peeling.

The test conditions and evaluation scale for the hot saltwater immersiontest were as follows. A cross cut was scribed with an acrylic cutter inthe sheet after operation (8) as described above, and the specimen thusprepared was immersed for 240 hours in a 5% by weight solution of sodiumchloride in water that was maintained at 55° C. and was bubbled withair. The specimen was allowed to stand for 1 hour after withdrawal fromthe saltwater bath, after which time the cross cut was peeled with tapeand the width of peeling from the cut was evaluated. The peelingbehavior was evaluated using the following three-level scale:

For the CRS:

++: maximum peel width (both sides) less than 4 mm;

+: maximum peel width (both sides) at least 4 mm but less than 6 mm;

x: maximum peel width (both sides) at least 6 mm.

For the EG: and GA:

++: maximum peel width (one side) less than 3 mm;

+: maximum peel width (one side) at least 3 mm but less than 5 mm;

x: maximum peel width (one side) at least 5 mm.

The test conditions and evaluation scale for salt spray testing were asfollows: A cross cut was scribed with an acrylic cutter in the sheetafter operation (8) as described above, and the specimen thus preparedwas tested using a salt spray tester (5% by weight solution of sodiumchloride in water) maintained at 35° C. After the stipulated time (basedon Japanese Industrial Standard Z-2371), the specimen was rinsed withwater and the status of corrosion at the cross cut was evaluated usingthe following three-level scale:

For the CRS (salt spray test time=960 hours):

++: maximum rust width (both sides) less than 4 mm;

+: maximum rust width (both sides) at least 4 mm but less than 5 mm;

x: maximum rust width (both sides) at least 5 mm.

For the EG and GA (salt spray test time=480 hours):

++: maximum rust width (one side) less than 4 mm;

+: maximum rust width (one side) at least 4 mm but less than 5 mm;

x: maximum rust width (one side) at least 5 mm.

Details of the surface conditioning processes and phosphate treatmentprocesses for the Examples and Comparative Examples and thecorresponding test results are reported in the following tables, inwhich the following abbreviations are used:

for the phosphate salt component:

Zn2FeP2=Zn₂Fe(PO₄)₂.4H₂O

Zn3P2=Zn₃(PO₄)₂.4H₂O

Zn2CaP2=Zn₂Ca(PO₄)₂.4H₂O

for the surfactant component:

EO11NPE=polyoxyethylene (EO: 11) nonylphenol ether

for the phosphorus compounds:

ATMPA=aminotrinmethylenephosphonic acid

1-HEDPA=1-hydroxyethylidene1,1-diphosphonic acid

2-HEDPA=2-hydroxyethylidene-1,1-diphosphonic acid

EDATMPA=ethylenediaminetetramethylenephosphonic acid.

other:

Deg.=Degree

Polym.=Polymerization

Ex.=Example

Comp. Ex.=Comparative Example

VA=vinyl acetate

PVAc=polyvinylalcohol

Wt%=Percent by weight.

TABLE 1 EXAMPLES 1 TO 5 Example Number: 1 2 3 4 5 Surface ConditioningTreatment Composition Constituents and Process Conditions:PREPALENE ®-ZN, g/l none none none none none Phosphate Particles:Abbreviation Zn2FeP2 Zn2FeP2 Zn2FeP2 Zn2FeP2 Zn2FeP2 Particle size, μm0.5 0.5 0.5 0.5 0.5 Concentration, g/l 1 1 1 1 1 Saccharide-BasedConstituents: Monosaccharide Unit glucose glucose glucose glucosefructose Substituent(s) CH₂COOH CH₂COOH CH₂COOH none none NO₂ NO₂ Deg.of Substitution ≦1.8 ≦1.8 0.7 none 0 Deg. of Polym. ≦3,000 ≦3,000 ≦100 1≦100 Concentration, ppm 5 1,000 10 2,000 2,000 Salt constituent(s):Chemical Formula none none NaNO₂ MgSO₄. none 7H₂O Concentration, g/lnone none 0.5 0.5 none Surfactant Constituents: Abbreviation none nonenone none none Concentration, g/l none none none none none TreatmentTemperature, ° C. 20 20 20 20 20 Treatment Time, Seconds 30 30 30 30 30Phosphate Conversion Treatment Composition Constituents and ProcessConditions: Grams per Liter of: PO₄ ³⁻ 10 15 20 18 16 Zn²⁺ 0.8 1.3 2.21.5 1.4 Mg²⁺ 2.0 none none none 2.5 Co²⁺ none 1.0 none none none Mn²⁺0.5 none 1.0 none none Ca²⁺ none none none 1.5 none Sr²⁺ none none nonenone 0.9 WO₄ ⁻² none none 0.3 none none NO₃ ⁻ 8.3 7.6 9.0 8.0 7.3 F⁻ 0.1none 0.1 none 0.1 NO₂ ⁻ 0.01 none 0.01 none 0.01 NH₄OH none 1.5 none 3.0none Treatment Temperature, ° C. 40 45 50 35 43 Treatment Time, Seconds120 120 120 120 120

TABLE 2 EXAMPLES 6 TO 10 Example Number: 6 7 8 9 10 Surface ConditioningTreatment Composition Constituents and Process Conditions:PREPALENE ®-ZN, g/l none none none none none Phosphate Particles:Abbreviation Zn2FeP2 Zn3P2 Zn3P2 Zn2CaP2 Zn2CaP2 Particle size, μm 0.50.6 1.2 0.4 0.4 Concentration, g/l 1 1 1 10 5 Saccharide-BasedConstituents: Monosaccharide Unit glucose glucose glucose glucosefructose xylose galactose Substituent(s) none CH₂COOH CH₂COOH CH₂COOHnone CH₃ Deg. of Substitution 0 ≧2 1.9 1.0 0 Deg. of Polym. ≦500 ≦200≦1,000 ≦2,000 ≦500 Concentration, ppm 100 100 1 10 5 Saltconstituent(s): Chemical Formula none none Na₂O.SiO₂. Na₂CO₃ Na₃PO₄.5H₂O 12H₂O Concentration, g/l none none 5 1 10 Surfactant Constituents:Abbreviation none none none none EO11NPE Concentration, g/l none nonenone none 2.0 Treatment Temperature, ° C. 20 20 20 20 40 Treatment Time,Seconds 30 30 30 30 120 Phosphate Conversion Treatment CompositionConstituents and Process Conditions: Grams per Liter of: PO₄ ³⁻ 11 15 2218 16 Zn²⁺ 0.9 1.3 2.0 1.5 1.4 Mg²⁺ 2.0 none none none 2.5 Co²⁺ nonenone none none none Mn²⁺ 0.6 none 1.0 none none Ca²⁺ none none none 1.0none Sr²⁺ none none none none 0.9 WO₄ ⁻² none none 0.3 none none NO₃ ⁻8.9 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none 0.01 nonenone NH₄OH none 1.5 none 3.0 3.5 Treatment Temperature, ° C. 38 43 49 5559 Treatment Time, Seconds 120 120 120 120 120

TABLE 3 COMPARATIVE EXAMPLES 1 TO 5 Comparative Example Number: 1 2 3 45 Surface Conditioning Treatment Composition Constituents and ProcessConditions: PREPALENE ®-ZN, g/l none none none none none PhosphateParticles: Abbreviation Zn2FeP2 Zn3P2 Zn3P2 Zn3P2 Zn3P2 Particle size,μm 0.5 0.6 1.2 0.5 0.5 Concentration, g/l 1 1 1 1 1 Saccharide-BasedConstituents: Monosaccharide Unit glucose glucose glucose glucosefructose xylose galactose Substituent(s) none CH₂COOH CH₂COOH none noneCH₃ Deg. of Substitution 0 ≧2 1.9 none none Deg. of Polym. ≦500 ≦200≦1,000 1 ≦100 Concentration, ppm 100 100 1 2000 2000 Saltconstituent(s): Chemical Formula none none Na₂O.SiO₂. MgSO₄. none 5H₂O7H₂O Concentration, g/l none none 5 0.5 none Surfactant Constituents:Abbreviation none none none none none Concentration, g/l none none nonenone none Treatment Temperature, ° C. 20 20 20 20 20 Treatment Time,Seconds 30 30 30 30 30 Phosphate Conversion Treatment CompositionConstituents and Process Conditions: Grams per Liter of: PO₄ ³⁻ 11 151.0 18 16 Zn²⁺ 0.1 7.0 2.0 1.5 1.4 Mg²⁺ 2.0 none none none 2.5 Co²⁺ nonenone none none none Mn²⁺ 0.6 none 1.0 1.0 none Ca²⁺ none none none nonenone Sr²⁺ none none none 3.0 0.9 WO₄ ⁻² none none 0.3 none none NO₃ ⁻8.9 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none 0.01 nonenone NH₄OH none 1.5 none 3.0 3.5 Treatment Temperature, ° C. 38 43 49 5520 Treatment Time, Seconds 120 120 120 120 120

TABLE 4 COMPARATIVE EXAMPLES 6 TO 10 Comparative Example Number: 6 7 8 910 Surface Conditioning Treatment Composition Constituents and ProcessConditions: PREPALENE ®-ZN, g/l 1 none none none none PhosphateParticles: Abbreviation none Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Particle size,μm none 0.6 6.5 0.4 0.5 Concentration, g/l none 1 1 10 0.00001Saccharide-Based Constituents: Monosaccharide Unit none none glucoseglucose glucose Substituent(s) none none CH₂COOH CH₂COOH CH₂COOH CH₃Deg. of Substitution none none 1.9 1.0 0.7 Deg. of Polym. none none≦1,000 ≦2,000 ≦100 Concentration, ppm none none 1 5,000 10 Saltconstituent(s): Chemical Formula none none Na₂O.SiO₂. Na₂CO₃ NaNO₂ 5H₂OConcentration, g/l none none 5 1 0.5 Surfactant Constituents:Abbreviation none none none none none Concentration, g/l none none nonenone none Treatment Temperature, ° C. 20 20 20 20 20 Treatment Time,Seconds 30 30 30 30 30 Phosphate Conversion Treatment CompositionConstituents and Process Conditions: Grams per Liter of: PO₄ ³⁻ 11 15 2218 16 Zn²⁺ 0.9 1.3 2.0 1.5 1.4 Mg²⁺ 2.0 none none none 2.5 Co²⁺ nonenone none none none Mn²⁺ 0.6 none 1.0 none none Ca²⁺ none none none 1.0none Sr²⁺ none none none none 0.9 WO₄ ⁻² none none 0.3 none none NO₃ ⁻8.9 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none 0.01 nonenone NH₄OH none 1.5 none 3.0 3.5 Treatment Temperature, ° C. 40 45 50 3943 Treatment Time, Seconds 120 120 120 120 120

TABLE 5 APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTINGPERFORMANCE TESTING FOR EXAMPLES 1 THROUGH 10 SUBSTRATE EXAMPLE NUMBERTEST OR OTHER RATING TESTED 1 2 3 4 5 6 7 8 9 10 Coating AppearanceCRS + + + + + + + + + + EG + + + + + + + + + + GA + + + + + + + + + +Secondary (Water-Resistant) CRS ++ ++ ++ ++ ++ ++ ++ ++ ++ ++ AdherenceEG ++ ++ + ++ ++ ++ ++ + ++ ++ GA ++ ++ + ++ ++ ++ ++ + ++ ++ Resistanceto Hot Salt Water CRS ++ ++ ++ ++ + ++ + ++ ++ + EG ++ ++ ++ ++ ++ ++ +++ ++ ++ GA ++ ++ ++ ++ ++ ++ + ++ ++ ++ Resistance to Salt Spray CRS +++ ++ + + + + + ++ + EG ++ + ++ + ++ ++ + + ++ ++ GA ++ + ++ + ++ ++ + +++ ++

TABLE 6 APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTINGPERFORMANCE TESTING FOR COMPARISON EXAMPLES 1 THROUGH 10 SUBSTRATECOMPARISON EXAMPLE NUMBER TEST OR OTHER RATING TESTED 1 2 3 4 5 6 7 8 910 Coating Appearance CRS × + × × × + × × × × EG × + × × × + × × × + GA× + × × × + × × × + Secondary (Water-Resistant) CRS ++ + ++ ++ ++ + ++++ ++ + Adherence EG × × × × × × × × × × GA × × × × × × × × × ×Resistance to Hot Salt Water CRS × ++ × × × ++ × × × × EG × + × × × + ×× × + GA × + × × × + × × × + Resistance to Salt Spray CRS × × × × × × ×× × × EG × + × × × + × × × × GA × × × × × × × × × ×

TABLE 7 EXAMPLES 11 TO 15 Example Number: 11 12 13 14 15 SurfaceConditioning Treatment Composition Constituents and Process Conditions:PREPALENE ®-ZN, g/l none none none none none Phosphate Particles:Abbreviation Zn2FeP2 Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Particle size, μm 0.50.5 1.7 0.6 0.5 Concentration, g/l 5 1 1 5 10 Phosphorus ContainingSolute: Substance tripoly- hexameta- ATMPA 1-HEDPA EDATMPA phosphoricphosphoric acid acid Concentration, ppm 1 100 500 50 1,000 Saltconstituent(s): Chemical Formula MgSO₄. Na₂O.SiO₂. none Na₂CO₃ Na₃PO₄.7H₂O 5H₂O 12H₂O Concentration, g/l 0.5 1 none 5 10 SurfactantConstituents: Abbreviation none none none none EO11NPE Concentration,g/l none none none none 2.0 Treatment Temperature, ° C. 20 20 20 20 40Treatment Time, Seconds 30 30 30 30 120 Phosphate Conversion TreatmentComposition Constituents and Process Conditions: Grams per Liter of: PO₄³⁻ 10 15 20 18 16 Zn²⁺ 0.8 1.3 2.2 1.5 1.4 Mg²⁺ 2.0 none none none 2.5Co²⁺ none 1.0 none none none Mn²⁺ 0.5 none 1.0 none none Ca²⁺ none nonenone 1.5 none Sr²⁺ none none none none 0.9 WO₄ ⁻² none none 0.3 nonenone NO₃ ⁻ 8.3 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none0.01 none 0.01 NH₄OH none 1.5 none 3.0 none Treatment Temperature, ° C.40 45 50 39 43 Treatment Time, Seconds 120 120 120 120 120

TABLE 8 COMPARATIVE EXAMPLES 11 TO 15 Comparative Example Number: 11 1213 14 15 Surface Conditioning Treatment Composition Constituents andProcess Conditions: PREPALENE ®-ZN, g/l none none none none nonePhosphate Particles: Abbreviation Zn2FeP2 Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2Particle size, μm 0.5 0.5 1.7 0.6 0.5 Concentration, g/l 5 1 1 5 10Phosphorus Containing Solute: Substance tripoly- hexameta- ATMPA 2-HEDPAEDATMPA phosphoric phosphoric acid acid Concentration, ppm 1 100 500 501,000 Salt constituent(s): Chemical Formula MgSO₄. NaOH none Na₂CO₃Na₃PO₄. 7H₂O 12H₂O Concentration, g/l 0.5 1 none 5 10 SurfactantConstituents: Abbreviation none none none none EO11NPE Concentration,g/l none none none none 2.0 Treatment Temperature, ° C. 20 20 20 20 40Treatment Time, Seconds 30 30 30 30 120 Phosphate Conversion TreatmentComposition Constituents and Process Conditions: Grams per Liter of: PO₄³⁻ 11 15 1.0 18 16 Zn²⁺ 0.1 7.0 2.0 1.5 1.4 Mg²⁺ 2.0 none none none 2.5Co²⁺ none none none none none Mn²⁺ 0.6 none 1.0 1.0 none Ca²⁺ none nonenone none none Sr²⁺ none none none 3.0 0.9 WO₄ ⁻² none none 0.3 nonenone NO₃ ⁻ 8.9 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none0.01 none none NH₄OH none 1.5 none 3.0 3.5 Treatment Temperature, ° C.40 45 50 39 20 Treatment Time, Seconds 120 120 120 120 120

TABLE 9 COMPARATIVE EXAMPLES 16 TO 20 Comparative Example Number: 16 1718 19 20 Surface Conditioning Treatment Composition Constituents andProcess Conditions: PREPALENE ®-ZN, g/l 1 none none none none PhosphateParticles Abbreviation none Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Particle size,μm none 0.5 6.5 0.6 0.00001 Concentration, g/l none 1 1 5 10 PhosphorusContaining Solute Substance none none ATMPA hexametaphos- EDATMPA phoricacid Concentration, ppm none none 500 3,000 1,000 Salt constituent(s)Chemical Formula MgSO₄. none none Na₂CO₃ Na₂O.SiO₂. 7H₂O 5H₂OConcentration, g/l 0.5 none none 5 1 Surfactant ConstituentsAbbreviation none none none none EO11NPE Concentration, g/l none nonenone none 2.0 Treatment Temperature, ° C. 20 20 20 20 40 Treatment Time,Seconds 30 30 30 30 120 Phosphate Conversion Treatment CompositionConstituents and Process Conditions: Grams per Liter of: PO₄ ³⁻ 11 15 2218 16 Zn²⁺ 0.9 1.3 2.0 1.5 1.4 Mg²⁺ 2.0 none none none 2.5 Co²⁺ nonenone none none none Mn²⁺ 0.6 none 1.0 none none Ca²⁺ none none none 1.0none Sr²⁺ none none none none 0.9 WO₄ ⁻² none none 0.3 none none NO₃ ⁻8.9 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none 0.01 nonenone NH₄OH none 1.5 none 3.0 3.5 Treatment Temperature, ° C. 40 45 50 3943 Treatment Time, Seconds 120 120 120 120 120

TABLE 10 APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTINGPERFORMANCE TESTING FOR EXAMPLES 11 THROUGH 15 TEST OR SUBSTRATE EXAMPLENUMBER OTHER RATING TESTED 11 12 13 14 15 Coating CRS + + + + +Appearance EG + + + + + GA + + + + + Secondary CRS ++ ++ ++ ++ ++(Water-Resistant) EG ++ ++ + ++ ++ Adherence GA ++ ++ + ++ ++ Resistanceto CRS ++ ++ ++ ++ + Hot Salt Water EG ++ ++ ++ ++ ++ GA ++ ++ ++ ++ ++Resistance to CRS + ++ ++ + + Salt Spray EG ++ + ++ + ++ GA ++ + ++ + ++

TABLE 11 APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTINGPERFORMANCE TESTING FOR COMPARISON EXAMPLES 11 THROUGH 20 SUBSTRATECOMPARISON EXAMPLE NUMBER TEST OR OTHER RATING TESTED 11 12 13 14 15 1617 18 19 20 Coating Appearance CRS × + × × × + × × × × EG × + × × × + ×× × + GA × + × × × + × × × + Secondary (Water-Resistant) CRS ++ + ++ ++++ + ++ ++ ++ + Adherence EG × × × × × × × × × × GA × × × × × × × × × ×Resistance to Hot Salt Water CRS × ++ × × × ++ × × × × EG × + × × × + ×× × + GA × + × × × + × × × + Resistance to Salt Spray CRS × × × × × × ×× × × EG × + × × × + × × × × GA × × × × × × × × × ×

TABLE 12 EXAMPLES 16 TO 20 Example Number: 16 17 18 19 20 SurfaceConditioning Treatment Composition Constituents and Process Conditions:PREPALENE ®-ZN, g/l none none none none none Phosphate ParticlesAbbreviation Zn2FeP2 Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Particle size, μm 0.51.5 0.5 1.6 0.3 Concentration, g/l 5 8 1 5 10 Water Soluble VA Polymeror Derivative Substance Name polyvinyl carboxyl- sulfonic CopolymerCopolymer alcohol modified acid- with VA with VA PV Alc modified PV AlcComonomer with VA none none none maleic crotonic acid acid Comonomer %by Weight none none none 80 70 Concentration, ppm 1 500 2,000 1,000 10Salt constituent(s) Chemical Formula MgSO₄. Na₂O.SiO₂. none Na₂CO₃Na₃PO₄. 7H₂O 5H₂O 12H₂O Concentration, g/l 0.5 1 none 5 10 SurfactantConstituents Abbreviation none none none none EO11NPE Concentration, g/lnone none none none 2.0 Treatment Temperature, ° C. 20 20 20 20 40Treatment Time, Seconds 30 30 30 30 120 Phosphate Conversion TreatmentComposition Constituents and Process Conditions: Grams per Liter of: PO₄³⁻ 10 15 20 18 16 Zn²⁺ 0.8 1.3 2.2 1.5 1.4 Mg²⁺ 2.0 none none none 2.5Co²⁺ none 1.0 none none none Mn²⁺ 0.5 none 1.0 none none Ca²⁺ none nonenone 1.5 none Sr²⁺ none none none none 0.9 WO₄ ⁻² none none 0.3 nonenone NO₃ ⁻ 8.3 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none0.01 none 0.01 NH₄OH none 1.5 none 3.0 none Treatment Temperature, ° C.40 45 50 39 43 Treatment Time, Seconds 120 120 120 120 120

TABLE 13 COMPARATIVE EXAMPLES 21 TO 25 Comparative Example Number: 21 2223 24 25 Surface Conditioning Treatment Composition Constituents andProcess Conditions: PREPALENE ®-ZN, g/l none none none none nonePhosphate Particles: Abbreviation Zn2FeP2 Zn3P2 Zn3P2 Zn2CaP2 Zn3P2Particle size, μm 0.5 0.5 0.5 1.6 0.5 Concentration, g/l 5 1 1 5 1 WaterSoluble VA Polymer or Derivative: Substance Name polyvinyl- carboxyl-sulfonic Copolymer Copolymer alcohol modified acid- with VA with VA PVAlc modified PV Alc Comonomer with VA none none none maleic crotonicacid acid Comonomer % by Weight none none none 80 70 Concentration, ppm1 500 2,000 1,000 10 Salt constituent(s): Chemical Formula MgSO₄.Na₂O.SiO₂. none Na₂CO₃ Na₃PO₄. 7H₂O 5H₂O 12H₂O Concentration, g/l 0.5 1none 5 10 Surfactant Constituents: Abbreviation none none none noneEO11NPE Concentration, g/l none none none none 2.0 TreatmentTemperature, ° C. 20 20 20 20 40 Treatment Time, Seconds 30 30 30 30 120Phosphate Conversion Treatment Composition Constituents and ProcessConditions: Grams per Liter of: PO₄ ³⁻ 11 15 1.0 18 16 Zn²⁺ 0.1 7.0 2.01.5 1.4 Mg²⁺ 2.0 none none none 2.5 Co²⁺ none none none none none Mn²⁺0.6 none 1.0 1.0 none Ca²⁺ none none none none none Sr²⁺ none none none3.0 0.9 WO₄ ⁻² none none 0.3 none none NO₃ ⁻ 8.9 7.6 9.0 8.0 7.3 F⁻ 0.1none 0.1 none 0.1 NO₂ ⁻ 0.01 none 0.01 none none NH₄OH none 1.5 none 3.03.5 Treatment Temperature, ° C. 40 45 50 39 20 Treatment Time, Seconds120 120 120 120 120

TABLE 14 COMPARATIVE EXAMPLES 26 TO 30 Comparative Example Number: 26 2728 29 30 Surface Conditioning Treatment Composition Constituents andProcess Conditions: PREPALENE ®-ZN, g/l 1 none none none none PhosphateParticles: Abbreviation none Zn2FeP2 Zn3P2 Zn2CaP2 Zn2FeP2 Particlesize, μm none 1.7 6.5 1.6 0.3 Concentration, g/l none 7 1 5 0.00001Water Soluble VA Polymer or Derivative: Substance Name polyvinyl nonesulfonic Copolymer Copolymer alcohol acid- with VA with VA modified PVAlc Comonomer with VA none none none maleic crotonic acid acid Comonomer% by Weight none none none 80 70 Concentration, ppm 1 none 2,000 3,00010 Salt constituent(s): Chemical Formula none Na₂O.SiO₂. none Na₂CO₃Na₃PO₄. 5H₂O 12H₂O Concentration, g/l none 1 none 5 10 SurfactantConstituents: Abbreviation none none none none EO11NPE Concentration,g/l none none none none 2.0 Treatment Temperature, ° C. 20 20 20 20 40Treatment Time, Seconds 30 30 30 30 120 Phosphate Conversion TreatmentComposition Constituents and Process Conditions: Grams per Liter of: PO₄³⁻ 10 15 20 18 16 Zn²⁺ 0.8 1.3 2.2 1.5 1.4 Mg²⁺ 2.0 none none none 2.5Co²⁺ none 1.0 none none none Mn²⁺ 0.5 none 1.0 none none Ca²⁺ none nonenone 1.5 none Sr²⁺ none none none none 0.9 WO₄ ⁻² none none 0.3 nonenone NO₃ ⁻ 8.3 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none0.01 none 0.01 NH₄OH none 1.5 none 3.0 none Treatment Temperature, ° C.40 45 50 39 43 Treatment Time, Seconds 120 120 120 120 120

TABLE 15 APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTINGPERFORMANCE TESTING FOR EXAMPLES 16 THROUGH 20 TEST OR SUBSTRATE EXAMPLENUMBER OTHER RATING TESTED 16 17 18 19 20 Coating CRS + + + + +Appearance EG + + + + + GA + + + + + Secondary CRS ++ ++ ++ ++ ++(Water-Resistant) EG ++ ++ + ++ ++ Adherence GA ++ ++ + ++ ++ Resistanceto CRS ++ ++ ++ ++ + Hot Salt Water EG ++ ++ ++ ++ ++ GA ++ ++ ++ ++ ++Resistance to CRS + ++ ++ + + Salt Spray EG ++ + ++ + ++ GA ++ + ++ + ++

TABLE 16 APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTINGPERFORMANCE TESTING FOR COMPARISON EXAMPLES 21 THROUGH 30 SUBSTRATECOMPARISON EXAMPLE NUMBER TEST OR OTHER RATING TESTED 21 22 23 24 25 2627 28 29 30 Coating Appearance CRS × + × × × + × × × × EG × + × × × + ×× × + GA × + × × × + × × × + Secondary (Water-Resistant) CRS ++ + ++ ++++ + ++ ++ ++ + Adherence EG × × × × × × × × × × GA × × × × × × × × × ×Resistance to Hot Salt Water CRS × ++ × × × ++ × × × × EG × + × × × + ×× × + GA × + × × × + × × × + Resistance to Salt Spray CRS × × × × × × ×× × × EG × + × × × + × × × × GA × × × × × × × × × ×

TABLE 17 EXAMPLES 21 TO 25 with Type (4) Polymer Adhesion PromotingAgents Example Number: 21 22 23 24 25 Surface Conditioning TreatmentComposition Constituents and Process Conditions: PREPALENE ®-ZN, g/lnone none none none none Phosphate Particles Abbreviation Zn2FeP2 Zn3P2Zn3P2 Zn2CaP2 Zn2FeP2 Particle size, μm 0.5 0.5 1.7 0.6 0.5Concentration, g/l 5 1 1 5 10 Monomer with Formula (I) R¹ H none noneCH₃ none R² C₂H₄OH none none C₃H₇OH none Wt % in Polymer 100 none none20 none Other Unsaturated Acid Monomer Monomer Name none maleic acrylicmaleic methacrylic acid acid acid acid Wt % in Polymer none 80 100 80 50Other Comonomer Monomer Name none vinyl none none styrene- acetatesulfonic acid Wt % in Polymer none 20 none none 50 PolymerConcentration, ppm 1 500 2,000 1,500 5 Salt constituent(s) ChemicalFormula MgSO₄. Na₂O.SiO₂. none KOH Na₃PO₄. 7H₂O 5H₂O 12H₂OConcentration, g/l 0.5 1 none 5 10 Surfactant Constituents Abbreviationnone none none none EO11NPE Concentration, g/l none none none none 2.0Treatment Temperature, ° C. 20 20 20 20 40 Treatment Time, Seconds 30 3030 30 120 Phosphate Conversion Treatment Composition Constituents andProcess Conditions: Grams per Liter of: PO₄ ³⁻ 10 15 20 18 16 Zn²⁺ 0.81.3 2.2 1.5 1.4 Mg²⁺ 2.0 none none none 2.5 Co²⁺ none 1.0 none none noneMn²⁺ 0.5 none 1.0 none none Ca²⁺ none none none 1.5 none Sr²⁺ none nonenone none 0.9 WO₄ ⁻² none none 0.3 none none NO₃ ⁻ 8.3 7.6 9.0 8.0 7.3F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none 0.01 none 0.01 NH₄OH none 1.5none 3.0 none Treatment Temperature, ° C. 40 45 50 39 43 Treatment Time,Seconds 120 120 120 120 120

TABLE 18 COMPARATIVE EXAMPLES 31 TO 35 Comparative Example Number: 31 3233 34 35 Surface Conditioning Treatment Composition Constituents andProcess Conditions: PREPALENE ®-ZN, g/l none none none none nonePhosphate Particles Abbreviation Zn2FeP2 Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2Particle size, μm 0.5 0.5 1.7 0.6 0.5 Concentration, g/l 5 1 1 5 10Monomer with Formula (I) R¹ H none none CH₃ none R² C₂H₄OH none noneC₃H₇OH none Wt % in Polymer 100 none none 20 none Other Unsaturated AcidMonomer Monomer Name none maleic acrylic maleic methacrylic acid acidacid acid Wt % in Polymer none 80 100 80 50 Other Comonomer Monomer Namenone vinyl none none styrene- acetate sulfonic acid Wt % in Polymer none20 none none 50 Polymer Concentration, ppm 1 500 2,000 1,500 5 Saltconstituent(s) Chemical Formula MgSO₄. Na₂O.SiO₂. none Na₂CO₃ Na₃PO₄.7H₂O 5H₂O 12H₂O Concentration, g/l 0.5 1 none 5 10 SurfactantConstituents Abbreviation none none none none EO11NPE Concentration, g/lnone none none none 2.0 Treatment Temperature, ° C. 20 20 20 20 40Treatment Time, Seconds 30 30 30 30 120 Phosphate Conversion TreatmentComposition Constituents and Process Conditions: Grams per Liter of: PO₄³⁻ 11 15 1.0 18 16 Zn²⁺ 0.1 7.0 2.0 1.5 1.4 Mg²⁺ 2.0 none none none 2.5Co²⁺ none none none none none Mn²⁺ 0.6 none 1.0 1.0 none Ca²⁺ none nonenone none none Sr²⁺ none none none 3.0 0.9 WO₄ ⁻² none none 0.3 nonenone NO₃ ⁻ 8.9 7.6 9.0 8.0 7.3 F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none0.01 none none NH₄OH none 1.5 none 3.0 3.5 Treatment Temperature, ° C.40 45 50 39 20 Treatment Time, Seconds 120 120 120 120 120

TABLE 19 COMPARATIVE EXAMPLES 36 TO 40 Comparative Example Number: 36 3738 39 40 Surface Conditioning Treatment Composition Constituents andProcess Conditions: PREPALENE ®-ZN, g/l 1 none none none none PhosphateParticles Abbreviation none Zn2CaP2 Zn3P2 Zn2CaP2 Zn2FeP2 Particle size,μm none 0.8 6.8 0.6 0.5 Concentration, g/l none 10 1 5 0.0001 Monomerwith Formula (I) R¹ H none none CH₃ none R² C₂H₄OH none none C₃H₇OH noneWt % in Polymer 100 none none 20 none Other Unsaturated Acid MonomerMonomer Name none none acrylic maleic methacrylic acid acid acid Wt % inPolymer none none 100 80 50 Other Comonomer Monomer Name none none nonenone styrenesulfonic acid Wt % in Polymer none none none none 50 PolymerConcentration, ppm 1 none 2,000 3,000 5 Salt constituent(s) ChemicalFormula MgSO₄. Na₂O.SiO₂. none Na₂CO₃ Na₃PO₄. 7H₂O 5H₂O 12H₂OConcentration, g/l 0.5 1 none 5 10 Surfactant Constituents Abbreviationnone none none none EO11NPE Concentration, g/l none none none none 2.0Treatment Temperature, ° C. 20 20 20 20 40 Treatment Time, Seconds 30 3030 30 120 Phosphate Conversion Treatment Composition Constituents andProcess Conditions: Grams per Liter of: PO₄ ³⁻ 10 15 20 18 16 Zn²⁺ 0.81.3 2.2 1.5 1.4 Mg²⁺ 2.0 none none none 2.5 Co²⁺ none 1.0 none none noneMn²⁺ 0.5 none 1.0 none none Ca²⁺ none none none 1.5 none Sr²⁺ none nonenone none 0.9 WO₄ ⁻² none none 0.3 none none NO₃ ⁻ 8.3 7.6 9.0 8.0 7.3F⁻ 0.1 none 0.1 none 0.1 NO₂ ⁻ 0.01 none 0.01 none 0.01 NH₄OH none 1.5none 3.0 none Treatment Temperature, ° C. 40 45 50 39 43 Treatment Time,Seconds 120 120 120 120 120

TABLE 20 APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTINGPERFORMANCE TESTING FOR EXAMPLES 21 THROUGH 25 TEST OR SUBSTRATE EXAMPLENUMBER OTHER RATING TESTED 21 22 23 24 25 Coating CRS + + + + +Appearance EG + + + + + GA + + + + + Secondary CRS ++ ++ ++ ++ ++(Water-Resistant) EG ++ ++ + ++ ++ Adherence GA ++ ++ + ++ ++ Resistanceto CRS ++ ++ ++ ++ + Hot Salt Water EG ++ ++ ++ ++ ++ GA ++ ++ ++ ++ ++Resistance to CRS + ++ ++ + + Salt Spray EG ++ + ++ + ++ GA ++ + ++ + ++

TABLE 21 APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTINGPERFORMANCE TESTING FOR COMPARISON EXAMPLES 31 THROUGH 40 SUBSTRATECOMPARISON EXAMPLE NUMBER TEST OR OTHER RATING TESTED 31 32 33 34 35 3637 38 39 40 Coating Appearance CRS × + × × × + × × × × EG × + × × × + ×× × + GA × + × × × + × × × + Secondary (Water-Resistant) CRS ++ + ++ ++++ + ++ ++ ++ + Adherence EG × × × × × × × × × × GA × × × × × × × × × ×Resistance to Hot Salt Water CRS × ++ × × × ++ × × × × EG × + × × × + ×× × + GA × + × × × + × × × + Resistance to Salt Spray CRS × × × × × × ×× × × EG × + × × × + × × × × GA × × × × × × × × × ×

What is claimed is:
 1. A process for forming a phosphate conversioncoating on a metal substrate surface, said process comprising thefollowing operations: (I) contacting the metal substrate surface with anaqueous liquid surface conditioning composition that comprises water andthe following components: (I.A) dispersed solid phosphate particlesthat: (i) have a diameter no greater than 5 μm; and (ii) comprise atleast one substance selected from the group consisting of phosphatesthat contain at least one type of divalent or trivalent metal cations;and (I.B) as adhesion-promoting component, at least one selection fromthe group consisting of the following subgroups: (1) monosaccharides,polysaccharides, and derivatives thereof; (2) phosphorus containingsolutes selected from the group consisting of orthophosphoric acid,condensed phosphoric acids, and organophosphonic acid compounds; (3)water-soluble polymers that are homopolymers or copolymers of vinylacetate and derivatives of these homopolymers and copolymers; and (4)copolymers and polymers afforded by the polymerization of: (a) at leastone selection from: monomers, exclusive of vinyl acetate, that conformto general chemical formula:

 where R¹=H or CH₃ and R²=H, C₁ to C₅ alkyl, or C₁ to C₅ hydroxyalkyl;and other α, β-unsaturated carboxylic acid monomers; and, optionally,(b) not more than 50% by weight of monomers that are not vinyl acetateand are not within the description of part (a) immediately above but arecopolymerizable with said monomers that are within the description ofsaid part (a); and (II) contacting the metal substrate surface asconditioned in operation (I) as described above with a nickel-freephosphate conversion treatment bath that comprises water and thefollowing amounts of the following components: (II.A) from 0.5 to 5 g/lof zinc cations; (II.B) from 5 to 30 g/l of phosphate ions; and (II.C) acomponent of conversion accelerator.
 2. A process according to claim 1,wherein the phosphate conversion treatment bath also contains from 0.1to 3.0 g/l of at least one type of ions selected from the groupconsisting of magnesium ions, cobalt ions, manganese ions, calcium ions,tungstate ions, and strontium ions.
 3. A process according to claim 2,wherein the concentration of component (1.A) is from 0.001 to 30 g/l andthe concentration of component (1.B) is form 1 to 2,000 ppm.
 4. Aprocess according to claim 1, wherein the concentration of component(1.A) is from 0.001 to 30 g/l and the concentration of component (1.B)is from 1 to 2,000 ppm.
 5. The process of claim 1 wherein the divalentor trivalent metal cations are selected from the group consisting of Zn,Fe, Mn, Co, Ca, Mg and Al.
 6. The process of claim 1 wherein the aqueousliquid surface conditioning composition has a concentration of dispersedsolid phosphate particles of from 0.001 to 30 g/l.
 7. The process ofclaim 1 wherein the aqueous liquid surface conditioning composition hasa concentration of adhesion-promoting component of from 1 to 2000 ppm.8. The process of claim 1 wherein the aqueous liquid surfaceconditioning composition is additionally comprised of an alkali metal orammonium salt selected from the group consisting of orthophosphatesalts, metaphosphate salts, orthosilicate salts, metasilicate salts,carbonate salts, bicarbonate salts, nitrate salts, nitrite salts,sulfate salts, borate salts, organic acid salts and mixtures thereof. 9.The process of claim 1 wherein the nickel-free phosphate conversiontreatment bath is additionally comprised of an etchant selected from thegroup consisting of fluoride ions, complex fluoride ions, and mixturesthereof.
 10. The process of claim 1 wherein the metal substrate isselected from the group consisting of steel sheets, zinc-plated steelsheets, zinc alloy-plated steel sheets, magnesium alloys, and aluminumalloys.